Amorphous, soluble, aromatic polymers with high glass transition temperatures

Abstract

Amorphous polymers which are soluble in organic solvents and can thus be cast as films have high glass transition temperatures which make them suitable for numerous high temperature applications; the polymers comprise ortho aromatic polyketones, polyphthalazines and polyisoquinolines, the polyphthalazines and polyisoquinolines being readily formed from the polyketones.

We claim: 
     
       1. An amorphous polymer of formula (I): ##STR36## wherein A 1 , A 2 , A 3  and A 4  are each independently selected from hydrogen, aryl selected from the group consisting of phenyl, naphthyl and anthracyl, diphenylether or heteroaromatic radicals selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl, said aryl, diphenylether and heteroaromatic radicals being unsubstituted or substituted by a substituent selected from lower alkyl of 1 to 6 carbon atoms, lower alkoxy of 1 to 6 carbon atoms, lower thioalkyl of 1 to 6 carbon atoms, halogen, phenyl, naphthyl, anthracyl, diphenylether or heteroaromatic radicals selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl, B and D are both carbonyl groups CO, or   B and D together represent a divalent radical of formula: ##STR37##  wherein Ar 3  is an aryl selected from the group consisting of phenyl, naphthyl and anthracyl, diphenylether or heteroaromatic radical selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl, unsubstituted or substituted by a substituent selected from lower alkyl of 1 to 6 carbon atoms, lower alkoxy of 1 to 6 carbon atoms, lower thioalkyl of 1 to 6 carbon atoms, halogen, phenyl, naphthyl, anthracyl, diphenylether or heteroaromatic radicals selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl,   Ar 1  and Ar 2  are each phenylene radicals, unsubstituted or substituted 1 to 4 times by a substituent selected from lower alkyl of 1 to 6 carbon atoms, lower alkoxy of 1 to 6 carbon atoms, lower thioalkyl of 1 to 6 carbon atoms, halogen, phenyl, naphthyl, anthracyl, diphenylether or heteroaromatic radicals selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl,   n is an integer of 20 to 200,   X is a single bond, --O--R--O, --S-- or --S--R--S--, wherein R is arylene selected from the group consisting of phenylene, naphthylene and anthracylene or aralkylidinylarylene of formula   --Ph--R.sub.1 --Ph--        in which R 1  is a straight chain or branched alkylene of 1 to 6 carbon atoms and Ph is phenylene, in which each arylene and phenylene moiety is unsubstituted or substituted by lower alkyl of 1 to 6 carbon atoms, lower alkoxy of 1 to 6 carbon atoms, lower thioalkyl of 1 to 6 carbon atoms, halogen, phenyl, naphthyl, anthracyl, diphenylether or heteroaromatic radicals selected from the group consisting of pyridinyl, pyrazinyl, quinolinyl, thiophenyl, benzothiophenyl, furanyl and dibenzofuranyl, and the alkylidine moiety of said aralkylidinylarylene is unsubstituted or fluoro-substituted alkylidine,   said polymer having a glass transition temperature of at least 220° C.,   and provided that when B and D are both carbonyl groups CO, A 1  and A 4  are both selected from said aryl, diphenylether or heteroaromatic radicals.   
     
     
       2. A polymer of claim 1 in which B and D are both carbonyl groups. 
     
     
       3. A polymer of claim 1 in which B and D represent said divalent radical of formula (II) whereby B and D form part of a pyridazine ring. 
     
     
       4. A polymer of claim 1 in which B and D represent said divalent radical of formula (III), whereby B and D form part of a pyridine ring. 
     
     
       5. A polyketone of claim 2 wherein A 2  and A 3  are each independently selected from hydrogen and phenyl, A 1  and A 4  are both phenyl and X is selected from OPhC(CH 3 ) 2  PhO, OPhO and OPhPhO in which Ph is phenylene. 
     
     
       6. A polyphthalazine of claim 3 wherein A 1 , A 2 , A 3  and A 4  are each independently selected from hydrogen and phenyl and X is --O--R--O in which R is selected from OPhC(CH 3 ) 2  PhO, and OPhPhO in which Ph is phenylene. 
     
     
       7. A polyisoquinoline of claim 4 wherein A 1 , A 2 , A 3  and A 4  are each independently selected from hydrogen and phenyl and X is --O--R--O in which R is selected from OPhC(CH 3 ) 2  PhO, OPhO and OPhPhO in which Ph is phenylene; and Ar 3  is phenyl. 
     
     
       8. A polyketone of claim 2 wherein A 2  and A 3  are each independently selected from hydrogen or phenyl and A 1  and A 4  are both phenyl. 
     
     
       9. A polyketone of claim 8 wherein A 2  and A 3  are both hydrogen. 
     
     
       10. A polyketone of claim 8 wherein A 2  and A 3  are both phenyl.